Ni/Pd/Si固相反应及NiSi热稳定性增强研究

研究了Ni/Pd双层薄膜在硅衬底上的硅化物形成过程.结果表明,加入Pd层后,退火形成Ni1-xPdxSi固熔体,该固熔体比NiSi的热稳定性好,使得NiSi向NiSi2的转变温度升高.加入Pd的量越多,NiSi2的成核温度越高,并用经典成核理论解释了该现象.     

Fifteen-Nanometer Ru Diffusion Barrier on NiSi/Si for a sub-45 nm Cu Contact Plug

A ruthenium film on a NiSi/Si substrate was evaluated for barrier performance in Cu contact metallization. The films were deposited by magnetron sputtering using Ni, Ru, and Cu targets. The low-resistivity NiSi film was initially produced from an Ni/Si substrate, and Ru and Cu films were sequentially deposited on the NiSi/Si substrate so that barrier performance could be studied. Barrier properties were elucidated by four-point probe measurement, x-ray diffractometry, scanning electron microscopy, Auger electron spectroscopy, and transmission electron microscopy. The stability temperatures of 600°C (Cu/NiSi/Si) and 650°C (Cu/Ru/NiSi/Si) were systematically verified and are discussed. Structural analysis indicated that the failure mechanism involved penetration of the Cu through the Ru/NiSi stacked film at a specific temperature, which induced the accelerated dissociation of the NiSi. Interposition of an Ru layer between the Cu and the NiSi/Si effectively prevented intermixing and substantially improved the thermal stability in the Cu/NiSi/Si stack films.     

Improved thermal stability of Ni-silicides on Si:C epitaxial layers

The thermal stability of Ni-silicides on tensily strained in situ P doped Si:C epitaxial layers was evaluated. The baseline Ni silicidation process was shown to be compatible with Si:C Recessed Source-Drain (RSD) stressors for NMOS strain engineering while the thermal stability of NiSi:C contacts was significantly improved compared to NiSi ones. Dominant degradation mechanism was shown to be the transition to the NiSi₂:C phase. It was demonstrated that the Si:C strain level affects the silicide formation but has no significant effect on the NiSi:C thermal stability. A mechanism responsible for the improved thermal stability of NiSi:C silicides is discussed.     

Study of NiSi/Si Interface by Cross-Section Transmission Electron Microscopy

采用不同硅化工艺制备了NiSi薄膜并用剖面透射电镜(XTEM)对样品的NiSi/Si界面进行了研究.在未掺杂和掺杂(包括As和B)的硅衬底上通过物理溅射淀积Ni薄膜,经快速热处理过程(RTP)完成硅化反应.X射线衍射和喇曼散射谱分析表明在各种样品中都形成了NiSi.还研究了硅衬底掺杂和退火过程对NiSi/Si界面的影响.研究表明:使用一步RTP形成NiSi的硅化工艺,在未掺杂和掺As的硅衬底上,NiSi/Si界面较粗糙;而使用两步RTP形成NiSi所对应的NiSi/Si界面要比一步RTP的平坦得多.高分辨率XTEM分析表明,在所有样品中都形成了沿衬底硅〈111〉方向的轴延-NiSi薄膜中的一些特定晶面与衬底硅中的(111)面对准生长.同时讨论了轴延中的晶面失配问题.     

NiSi/Si界面的剖面透射电镜研究

采用不同硅化工艺制备了NiSi薄膜并用剖面透射电镜(XTEM)对样品的NiSi/Si界面进行了研究.在未掺杂和掺杂(包括As和B)的硅衬底上通过物理溅射淀积Ni薄膜,经快速热处理过程(RTP)完成硅化反应.X射线衍射和喇曼散射谱分析表明在各种样品中都形成了NiSi.还研究了硅衬底掺杂和退火过程对NiSi/Si界面的影响.研究表明:使用一步RTP形成NiSi的硅化工艺,在未掺杂和掺As的硅衬底上,NiSi/Si界面较粗糙;而使用两步RTP形成NiSi所对应的NiSi/Si界面要比一步RTP的平坦得多.高分辨率XTEM分析表明,在所有样品中都形成了沿衬底硅〈111〉方向的轴延-NiSi薄膜中的一些特定晶面与衬底硅中的(111)面对准生长.同时讨论了轴延中的晶面失配问题.     

Pt层对Ni/Si(100)固相反应NiSi薄膜高温稳定性的增强效应

研究了顺次淀积在Si(100)衬底上的Ni/Pt和Pt/Ni的固相硅化反应．研究发现,当1nm Pt作为中间层或覆盖层加入Ni/Si体系中时,延缓了NiSi向NiSi2的转变,相变温度提高．对于这种双层薄膜体系,800℃退火后,XRD测试未检测到NiSi2相存在;850℃退火后的薄膜仍有一些NiSi衍射峰存在．800℃退火后的薄膜呈现较低的电阻率,在23—25μΩ*cm范围．上述薄膜较Ni/Si直接反应生成膜的热稳定性提高了100℃以上．这有利于NiSi薄膜材料在Si基器件制造中的应用．     

The effect of Si addition and Ta diffusion barrier on growth and thermal stability of NiSi nanolayer

Formation and thermal stability of nanothickness NiSi layer in Ni(Pt 4 at.%)/Si(1 0 0) and Ni_0.6Si_0.4(Pt 4 at.%)/Si(1 0 0) structures have been investigated using magnetron co-sputtering deposition method. Moreover, to study the effect of Si substrate in formation of NiSi and its thermal stability, we have used Ta diffusion barrier between the Ni_0.6Si_0.4 layer and the Si substrate. Post annealing treatment of the samples was performed in an N₂ environment in a temperature range from 200 to 900 °C for 2 min. The samples were analyzed by four point probe sheet resistance (R_s) measurement, X-ray diffraction (XRD) and atomic force microscopy (AFM) techniques. It was found that the annealing process resulted in an agglomeration of the nanothickness Ni(Pt) layer, and consequently, phase formation of discontinuous NiSi grains at the temperatures greater than 700 °C. Instead, for the Ni_0.6Si_0.4(Pt)/Si structure, 100 °C excess temperature in both NiSi formation and agglomeration indicated that it can be considered as a more thermally stable structure as compared with the Ni(Pt 4 at.%)/Si(1 0 0) structure. XRD, AFM and R_s analyses confirmed formation of a continuous NiSi film with R_s value of 5 Ω/□ in a temperature range of 700−800 °C. Use of Ta diffusion barrier showed that the role of diffusion of Ni atoms into the Si substrate is essential in complete silicidation of a NiSi layer.     

Thermal stability of Ni silicide films on heavily doped n and p Si substrates

Electrical and structural properties of Ni silicide films formed at various temperatures ranged from 200 °C to 950 °C on both heavily doped n⁺ and p⁺ Si substrates were studied. It was found that surface morphology as well as the sheet resistance properties of the Ni silicide films formed on n⁺ and p⁺ Si substrates at the temperatures higher than 600 °C were very different. Agglomerations of Ni silicide films on n⁺ Si substrates begin to occur at around 600 °C while there is no agglomeration observed in Ni silicide films on p⁺ Si substrates up to a forming temperature of 700 °C. It was also found that the phase transition temperature from NiSi phase to NiSi₂ phase depend on substrate types; 900 °C for NiSi film on n⁺ Si substrate and 750 °C for NiSi film on p⁺ Si substrate, respectively. Our results show that the agglomeration is, especially, important factor in the process temperature dependency of the sheet resistance of Ni silicides formed on n⁺ Si substrates.     

Cu contact on NiSi/Si with thin Ru/TaN barrier

Thin Ru(5 nm)/TaN(15 nm) bi-layer was sputtered on the NiSi/Si substrate as a diffusion barrier in the copper contact structure. The barrier properties were investigated through X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), energy dispersive X-ray (EDX) and electrical measurement. The whole Cu/Ru/TaN/NiSi/Si structure has a good thermal stability until after annealing at 450 °C. The Schottky barrier measurement shows that the leakage current increases after 450 °C annealing and after 500 °C annealing the barrier fails. Failure mechanism of the barrier stack is discussed.     

Improvement of thermal stability of Ni silicide on N-Si by direct deposition of group III element (Al, B) thin film at Ni/Si interface

The direct deposition of a thin Al or B layer at Ni/Si interface was proposed as a new method to solve a problem of degraded thermal stability of Ni silicide on heavily doped N⁺-Si substrates. Significant improvement of thermal stability evaluated by the sheet resistance vs. silicidation temperature properties was observed. The improvement is attributed to suppression of agglomeration of the silicide layers. The Al layer was effective only when it was located at the Ni/Si interface before the silicidation process. The deposited Al and B layers under Ni layer segregated at the surface after the silicidation process. The use of B layer was preferable to control the phase transition from NiSi to NiSi₂.     

Dopant effects on the thermal stability of FUSI NiSi

The thermal stability of fully silicided (FUSI) NiSi with arsenic or boron doping on silicon on insulator (SOI) was investigated. After the stacks were subjected to a typical back-end of line (BEOL) thermal annealing in a N₂ ambient, abnormal oxidation of As doped FUSI NiSi stacks is observed by X-ray photoelectron spectroscopy (XPS), and confirmed by high-resolution transmission electron microscopy (HRTEM). X-ray diffraction (XRD) results show Ni-rich phases like Ni₃Si are formed due to abnormal oxidation of FUSI NiSi. In contrast to As doped stacks, no phase transformation nor abnormal oxidation are observed for B doped stacks under similar annealing. However, backside secondary ion mass spectrometry (SIMS) results indicate B penetration through a 3 nm SiON layer into the Si channel after N₂ annealing for 4 h at 400 °C. There is no evidence for Ni diffusion into the Si channel for B doped stacks. However, Ni penetration into the Si channel is observed for As doped stacks due to the enhancement of abnormal oxidation of FUSI NiSi.     

A Hafnium interlayer method to improve the thermal stability of NiSi film

The effect of a thin Hafnium interlayer on the thermal stability of NiSi film has been investigated. Both X-ray diffraction and Raman spectra show that no high resistivity NiSi₂ appears in the Hf-additioned films which were post-annealed at temperatures ranging from 600 °C to 800 °C. Auger electron spectroscopy and Rutherford back scattering show that the Hf interlayer has moved to the top of the film after rapid thermal annealing, working as the diffusion barrier for upper Ni atoms. The three-dimensional surface morphology by atom force microscopy shows that the agglomeration of NiSi is effectively suppressed, which is attributed to the barrier effect of the Hf interlayer. The fabricated Ni(Hf)Si/Si Schottky diodes still displays good current-voltage characteristics even after annealed at temperatures varied from 650 °C to 800 °C, which further show that the Hf interlayer can improve the thermal stability of NiSi.     

Thickness scaling issues of Ni silicide

Ni silicidation processes without a capping layer and with a TiN capping layer are studied from the point of view of process window, morphology of the resulting silicide, and mechanisms of degradation at higher temperatures. The thermal stability of NiSi films on As- and on B-doped (100) Si substrates was investigated for Ni film thicknesses ranging from 5 to 30 nm. While agglomeration was the mechanism of degradation for the thin films, both morphological changes and transformation to NiSi₂ were possible for thicker films depending on anneal temperature and time. Activation energy of 2.5 eV for NiSi on n+ (100) Si and p+ (100) Si was determined for the process of morphological degradation. The measured temperature and time dependences for the thermal degradation of NiSi films suggest that the activation energy for transformation to NiSi₂ is higher than for morphological degradation.     

Ni(W)Si/Si肖特基势垒二极管电学特性研究

文中首次提出在Ni中掺入夹层W的方法来提高NiSi的热稳定性。具有此结构的薄膜,经600℃～800℃快速热退火后,薄层电阻保持较低值,小于2Ω/□。经Raman光谱分析表明,薄膜中只存在NiSi相,而没有NiSi2生成。Ni(W)Si的薄层电阻由低阻转变为高阻的温度在800℃以上,比没有掺W的镍硅化物的转变温度的上限提高了100℃。Ni(W)Si/Si肖特基势垒二极管能够经受650℃～800℃不同温度的快速热退火,肖特基接触特性良好,肖特基势垒高度为0.65eV,理想因子接近于1。     

难熔夹层金属提高NiSi薄膜热稳定性的新思路

首次给出了一种具有规律性的能用来提高镍硅化物热稳定性的方法.依据此方法,摸索出在Ni中分别以夹层金属掺入Pt、Mo、Zr、W金属来提高NiSi硅化物的热稳定性.概括总结了掺人难熔金属M后形成的三元镍硅化物Ni(M)Si热稳定性能.实验结果表明,Ni(M)Si硅化物薄膜四种镍硅化物薄膜有相同的热稳定性.以Ni/W/Ni/...     

一种利用夹层Ta难熔金属提高NiSi薄膜热稳定性的新方法

本文首次给出了一种具有规律性的能用来提高镍硅化物热稳定性的方法.依据此方法,首次摸索出在Ni中掺入夹层金属Ta来提高NiSi硅化物的热稳定性.Ni/Ta/Ni/Si样品经600 ～ 800℃快速热退火后,薄层电阻率保持较小值,约2Ω□.XRD衍射分析结果表明,在600～800℃快速热退火温度下形成的Ni(Ta)S薄膜中...     

The reaction characteristics of ultra-thin Ni films on undoped and doped Si (100)

Reaction characteristics of ultra-thin Ni films (5 nm and 10 nm) on undoped and highly doped (As-doped and B-doped) Si (100) substrates are investigated in this work. The sheet resistance (Rs) measurements confirm the existence of a NiSi salicidation process window with low Rs values within a certain annealing temperature range for all the samples except the one of Ni(5 nm) on P⁺-Si(100) substrate (abnormal sample). The experimental results also show that the transition reaction to low resistivity phase NiSi is retarded on highly doped Si substrates regardless of the initial Ni film thickness. Micro-Raman and x-ray diffraction (XRD) measurement show that NiSi forms in the process window and NiSi₂ forms in a higher temperature annealing process for all normal substrates. Auger electron spectroscopy (AES) results for the abnormal sample show that the high resistivity of the formation film is due to the formation of NiSi₂.     

Ni(Pt)Si硅化物温度稳定性的研究

对比研究了夹层结构N i/P t/N i分别与掺杂p型多晶硅和n型单晶硅进行快速热退火形成的硅化物薄膜的电学特性。实验结果表明,在600~800°C范围内,掺P t的N iS i薄膜电阻率低且均匀,比具有低电阻率的镍硅化物的温度范围扩大了100~150°C。依据吉布斯自由能理论,对在N i(P t)S i薄膜中掺有2%和4%的P t样品进行了分析。结果表明,掺少量的P t可以推迟N iS i向N iS i2的转化温度,提高了镍硅化物的热稳定性。最后,制作了I-V特性良好的N i(P t)S i/S i肖特基势垒二极管,更进一步证明了掺少量的P t改善了N iS i肖特基二极管的稳定性。     

Electrical characteristics of thin Ni2Si,NiSi, and NiSi2 layers grown on silicon

We have determined the resistivity, carrier concentration, and Hall mobility as a function of thickness (700–3000 Å) of Ni₂Si, NiSi, and NiSi₂ layers formed by vacuum annealing at 270÷v300°C, ≈ 400°C, and ≈ 800°C, respectively, of nickel films vacuum-deposited on a silicon substrate (111 n-type and 100 p-type Si ρ ≈ 1KΩ). The layer thicknesses were measured by 2 MeV⁴He⁺ backscattering spectrometry. The silicide phase was confirmed by x-ray measurements. The electrical measurements were carried out using van der Pauw configuration. We found the electrical transport parameters to be independent of the film thickness within the experimental uncertainty. The Hall factors were assumed to be unity. The majority carriers are electrons in NiSi and holes in Ni₂Si and NiSi₂. The resistivity values are 24±2, 14±1, and 34±2 μΩcm, the electron concentrations are 9±3, 10 and 7±1, and ≈ 2 × 10²² cm^?3, and the Hall mobilities are 3±1, ≈ 4.5 and 6, and ≈ 9 cm²/Vs for Ni₂Si, NiSi (〈100〉 and 〈111〉), and NiSi₂, respectively. The systematic error in the measured values caused by currents in the high resistivity substrate is estimated to be less than 6% for the Hall coefficient. The results show that Ni₂Si, NiSi, and NiSi₂ layers formed by a thin film reaction are electrically metallic conductors, a result which concurs with those reported previously (1) for refractory metal silicides. The Hall mobility increases with the Si content in the silicide. The electron concentration is lowest for NiSi₂ leading to the highest resistivity for the epitaxial phase of NiSi₂.     

Structural and electrical characterization of platinum (~15 at%) doped nickel silicides on Si(100) and SiGe/Si(100) substrates

Ni(Pt~15 at%)Si/Si(100) and Ni(Pt~15 at%)SiGe/SiGe/Si(100) films corresponding to rapid thermal annealing (RTA1) temperatures of 220, 230 and 240 °C with constant RTA2 (at 420 °C) have been investigated for sub 20 nm devices. X-ray reflectometry (XRR), X-ray diffraction (XRD), four point probe, and atomic force microscopy (AFM) techniques were employed for the characterization of NiSi and NiSiGe films. XRR results indicated that NiSi and NiSiGe film thicknesses increased with RTA1 temperatures. NiSi films densities increased with layer thickness but NiSiGe films displayed an opposite trend. The diffractograms revealed that NiSi and NiSiGe layers contain identical phases and possessed fiber texture at 220 °C. Whereas, the peaks shift were observed for NiSi (211) and NiSi (021) at higher RTA1 temperatures which appear due to Pt diffusion (hexagonal structures of larger grain size were noted). NiSiGe crystallites self-alignment was observed because of strained SiGe/Si(100) substrate. At 240 °C, NiSiGe layer showed the smallest crystallites. This is believed to be due to Pt distributed along the silicide grain boundaries which obstructs silicide grain growth. NiSi and NiSiGe sheet resistance decreased significantly with increase in RTA1 temperatures and found to correlate with multiple grain orientation. AFM revealed a smooth-stable surface morphology for all films.